Statistical analysis of grain growth based on the Frieser-Eger film on development kinetics

Rochester Institute of Technology

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Theses

Thesis/Dissertation Collections

1973

Statistical analysis of grain growth based on the

Frieser-Eger film on development kinetics

Noreen Vredenburg

Sharon Perry

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Recommended Citation

STATISTICAL ANALYSIS OF GRAIN GROWTH

BASED

ON THE FRIESER-EGER FILM ON DEVELOPMENT KINETICS

hy

Noreen

Vredenhurg

Sharon L.

Perry

A thesis submitted in partial fulfillment of the

requirements for the degree of Bachelor.'of^-Science -inhthe College of Photographic Arts and Science

of the Rochester Institute of

Technology

June,

1973

Thesis

11

TABLE OF CONTENTS

Abstract

Pages.::

1-2

Acknowledgements

Page

<

11

Introduction

Pages

1-3

Chapter

#1

Exper1mental Procedure

Pages

4-8

Chapter #2 Experimental Results

Page

9-

22

Chapter

#3

Summary and Conclusions

Pages 23-25

LIST OF FIGURES

Fig.

#1

Grain Size Distribution Page 10

H2Q

with

20g.

sulfite per liter

Fig.

#2

Grain Size Distribution Page 11

H2Q

with

0.5g.

sulfite per liter

i-Fig.

#3

0.5

sulfite-inltiation period _Page 12

Fig.

#4

0.5g.

sulfite-comp. dev. period _Page

13

Fig.

#5

20.

g. sulfite-inltiation period Page 14

Fig.

#6

20.g. sulfite-comp.

dev.

period Page

15

Fig.

#7

Density

vs. Relative _og exposure Page 16

0.5g.

sulfite per liter

Fig.

#8

Density

vs. Relative og exposure Page

17

20g.

sulfite per liter

Fig.

#9

ANOVA Page 18

Fig.

#10

ANOVA Page 18

Fig.

#11

ANOVA Page

19

Fig.

#12

ANOVA Page

19

Fig.

#13

ANOVA Page 20

Fig.

#14

ANOVA Page 20

Fig.

#15

Mechanism of litho developer Page 21 [image:4.555.69.485.160.633.2]

ABSTRACT

Data were obtained from the Frleser-Eger film on

develop

ment kinetics for Initiation times and for total development

times of individual grains

(times

of complete

development)

in a lithographic developer and in a hydroquinone developer

with normal sulfite level. Approximate areas were computed

for each grain. The purpose of this investigation was to

compare the process of deveTLopment at the two sulfite levels

and to determine if there is a functional _relationship bet

ween total development time and grain size. Different rela

tionships were expected for the two types of developers. This

data analysis permits a better understanding of the differences

between lithographic and normal hydroquinone developers.

The data were obtained

by

observing a number of grains through

out the development process. The film was run through the

projector one frame at a time and each frame was counted so

that the initiation times and times of complete development

could be

determined.

The location of the grains In question

was maintained

by

means of a grid. The areas were measured

using the geometric shape Of the individual grains. The -shape

There were no functional relationships between grain size

and times of complete development or initiation times for

the two

developers.

There was,

however,

a significant

difference between the two developers with respect to

Initiation

times.

The initiation period for the

0.5

g.

sulfite developer Is shorter than the

20g.

sulfite developers

Initiation period. This difference is believed to be the

result of different development mechanisms for the developers,

The results of this evaluation are useful _only as an example

of a possible statistical analysis for films of a similar

ACKNOWLEDGEMENTS

We would like to express our special thanks to our _advisor,

Dr.

Burt Carroll who has helped us throughout our thesis.

Also,

a special thank-you goes to Rochester's DuPont

Photo-Products Plant for computer time and cooperation and The

INTRODUCTION

The process of development is often considered to exist in

two phases. The first phase or initiation period is the

initial stage of the reduction in which no _{microscopically}

visible reduction of the grain is apparent. The second

phase or completion period of a grain is the _{microscopically}

visible growth of silver in the grain until no further silver

growth is visible.

Meidinger"

studied the kinetics of development of large

individual silver bromide grains.

Microscopically,

he deter

mined the Initiation period and the rate of completion of

development through-out a _grain. He observed a decrease in

initiation period with increase in exposure until a maximum

was reached. The completion rate was independent of _exposure.

Both initiation period and completion rate decreased with in

creased bromide concentration in the

developer.

Both increased

with increases In pH of the developer and both decreased when

the developer was diluted with water. He found that the rate

of propagation of developments throughout the grain varied with

Freiser and Eger studied the process of development

by

using

infra-red microcinematography. The purpose of his investiga

tion was to obtain qualitive information _regarding photo

graphic

development.

Eger investigated several different

developers.

Extended work on two of the developers Frieser

and Eger used are studied in our thesis to obtain quantitative

data.

The first was a litho type developer and the second was a

normal hydroquinone

developer.

The _only difference in the

two

being

the amount of sulfite present. The litho type con

tains

0.5g

of sulfite per liter and the normal hydroquinone

developer contains 20.0 _g of sulfite per

liter.

These two

developers were selected for comparisons of initiation

periods and periods of complete

development.

The data was

collected so that any functional relationship between grain

sizes and initiation periods and complete _{development times}

could be detected and differences between developers.

The sulfite content of a developer can change the developers

properties. The sulfite in a hydroquinone black and white

developer usually reacts with the oxidation products

(quinone)

to form sulfonates. These oxidation products _usually have an

undesirable Influence throughout

development,

therefore the

sulfite acts as a preservative for hydroquinone and its

de-rlvitives. Sulfite can have three

functions;

_{preservative,}

The sulfite concentration in graphic arts developers is kept

very low in order to utilize

the

phenomenon known as "infec

tious development"

(the

more rapid

development

of grains In

the immediate neighborhood of _already

developing

grains).

Frotschen1

in

1937

proposed that infectious development was

due to the catalytic effect of oxidation _products. Yule11

postulated that the active catalyst was the semiquinone. The

semiquinone concentration can build _{up only} at low sulfite

concentrations. The

developing

reaction is autocatalytic under

these conditions. Yule11 believes that the semiquinone is

considerable stable

by

absorption on to the silver halide

grain. This provides the right environment for infectious

development.

Some compromise _concerning sulfite concentration in a graphic

arts developer is needed in order to obtain "good" dot quality

In a graphic arts _film. At low sulfite _{concentration,} the

lateral diffusion of hydroquinone oxidation products from the

exposed area to

developing

grains leads to _spreading of the

dot

image,

as well as

Increasing

the

density

within the

dot.

If the sulfite is completely absent, the excessive diffusion

of oxidation products results in a large spread of the

dot.

The compromise sulfite concentration must .be such that infec

tious development is promoted within the .dot

image,

without

any appreciable spread beyond the exposed area. Yule11 found

this compromise sulfite concentration to be around

lg.

per

EXPERIMENTAL PROCEDURE

A l6mm Kodak Pagent Projector was modified so that the film

could be advanced one frame at a time

by turning

a crank.

As each frame was advanced, a _counter was also advanced to

keep

track of the total number of frames that have been

examined.

Thus,

initiation periods and periods of complete

development can be measured in terms of the number of frames

and

by dividing by

the number of frames exposed per _second,

we can calculate the times.

The projector was set _up on a bench so that the image could

be projected on the wall _giving a projected image size of

diameter

11.5

Inches. The grains in question were located

oh a grid. The grid was 12 x 12 inches and divided into 1

inch squares. The grids were made on

97$

reflectance, white

cards. The grains in question were then outlined with

marking pen and numbered. One grid was made for each run.

The grains selected for use in this analysis had to meet the

following

specification:

1)

the grains must be _completely

in

focus,

and

2)

the grains must not _overlap or have a common

border.

These stipulations were _necessary to avoid

or the possibility that with a _slightly out of focus grain,

a development site might not be visible.

Many

grains had to

be dropped from the analysis because

they

could not meet the

requirements.

The approximate area for each grain was computed

by

_using

the area formula for its geometric _{shape, circular,} trian

gular or

hexagonal.

All measurements were made _using

drafting

dividers.

These measurements were made _using the outer edge

of the grains. For grains with irregular shapes, approxima

tions were made. That

is,

irregular shaped grains were called

either

triangles,

circles or

hexagons,

whichever it most

closely resembled.

Every

grain in question was examined in the frame before

pro-gressing to the next frame. It was noted that Just prior to

the appearance of a development site, some grains were covered

with a neutral

density

"cloud".

We can find no explanation

for this occurance.

It was noted

during

the examination of the

20g.

of sulfite

hydroquinone

developer,

that the runs _varied,In

length.

The

runs and lengths are shown in the tables below.

20g.

sulfite

hydroquinine

developer.

t ,

Run 1

7

ft.

Run 2

6

ft.

Run

3

19

ft.

0.5g

sulfite

litho

developer

Run 1

6.5

ft.

Run 2

5

ft.

Run

3

6.5

ft.

Run

k

4.5

ft.

Drs.

Frieser and Eger were questioned, via

letter,

what the

problem might

be.

They

indicated that some of the fruns were

made at

3

frames per second and that others were made at

5

frames per second.

They

did not,

however,

know which were

done at.which frame rate. The film was then run through a

normal

l6mm.

projector and

by

_observing the "flicker" of the

film,

we were able to determine that 'the longer runs were

made at

5

frames per second.

It was also noted that some of the grains were .completely

developed at the first frame. This was accounted for

by

Drs.

Frieser and Eger.

They

said that the camera was not turned

on

Immediately

after the developer came in contact with the

grains.

They

estimate that a period of about 10 seconds

"elapsed before the camera was started. This necessitated

adding 10 seconds to each of' the initiation periods.. Since

this is only an approximation, this analysis can be used

only as an example of the method

by

which other such films can

be analyzed.

However,

the results within a single run are

The data that was collected were analyzed statistically.

Analysis of Variance

(ANOVA)

(Figs.

9-l4)

, best line of

fit curves

(Figs.

3-6),

and grain size distributions were

applied to the data

(Figs.

1 &

2).

An emulsion like that used In this film was prepared

by

Dr.

Burt Carroll. The emulsion Dr. Eger used for his thesis is

not _chemically sensitized and consists of larger than normal

grain sizes which are not typical of practical emulsions.

Sensitometric evaluation of this emulsion gave a macroscopic

view of the difference between developers as well as the ab

normality of the emulsion.

Film samples were exposed to a Kodak step tablet

by

means of

an EG & G sensitometer at 10~3 _seconds.

The developers were prepared as stated in Dr. Egers thesis.

The "normal"

hydroquinone developer was made _up with little

trouble.

However,

the pH was stated

by

Eger as

being

11.2

and was found to be 10.8. The film was processed without _any

adjustments for pH. The litho

developer,

however,

oxidized

almost immediately. It was prepared several times without

success. Dr. R. Francis was consulted and he suggested

pre-paring the developer in two parts. The first part was

2.5g

hydroquinone and

0.5g

sodium sulfite and water to make 500 ml,

The second part was

50.

Og

potassium carbonate and

l.Og

potas-slum bromide and water to make 500 ml. Both parts were made

in water at

70*

8

immediately

before use. The exposed strips were developed

for

30,

60,

90,

120 and 150 seconds with continuous rock

agitation. The process was as below

(at

70*

F)

:

Litho..* _{or normal developer}

30,

60,

_90.

120,

& 150 seconds

Water

Stop

Bath 30 seconds

Fixer

(F.

5)

2 minutes

Wash

(gentle

agitation)

25

minutes

Dry

at 100* F

Since the emulsion does not contain a

hardener,

care was

taken to avoid washing the emulsion off the

base.

The process

was repeated several

times,

but uniform images could not be

obtained. The

density

values for each step were read

by

means

EXPERIMENTAL RESULTS .

Grain size distributions

(Figs.

1 &

2)

were plotted for both

the litho and the "normal" _hydroquinone

developers.

These

distributions were _essentially the same

Indicating

that the

samples were adequate for _showing the grain size distribution

for the emulsion. When plotted on

log-log

paper

they

indi

cated a normal distribution.

Analysis of Variance

(ANOVA)

were run to determine whether or

not there was a significant difference between the runs for

each

developer,

between the various grain sizes and between

the two developers. Each ANOVA was run with respect to initia

tion period and with respect to period of complete development.

The results are shown in Figs-.

(9-14).

A computer program was used to plot the grain size _vs. initia

tion period data and to determine the best line of fit for the

data for the two

developers.

The same program was used for

the period of complete

development.

Again the program was run

for both

developers.

See Figs

{3-6)6

A development time series

(Dlotg

E)

was plotted from the sen

sitometric data obtained from the emultion prepared

by

Dr.

Burt Carroll. Figs

(7

&

8).

Pictures showing the different mechanisms of development

10'

Ei*L

i

G-RBlIU

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DISTRIBUTION

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18

ANOVA - FIG

#9

c*= .05

response variable = _initiation period

0.5g.

sulfite - hydroquinone developer

SOURCE SS

<

---hS

--RATIO SIGN.

Runs

884.3

3

294.8

1.85

no

Grain Size

485.8

k

121.5

.76 no

Interaction

866.5

12 72.2 .45 no

Error 9081.8

57

159.3

TOTAL 11.318.4 76

\

ANOVA - FIG

#10

oc= .05

response variable = _period of complete development

0.5g.

sulfite - hydroquinone developer

SOURCE SS

f

MS

.

RATIO

r "' SIGN.

Runs 718.4

3

239.5

2.07

no

Grain Size 959.2

4

239.8

2.07

no

Interaction

320.9

12

26.7

.23 no

Error

5316.3

46 115.6

19

ANOVA - FIG

#11

c=

.05

response variable = _{Initiation period} 20g. sulfite - hydroquinone developer

~* " --"' - ,

SOURCE SS

X

MS

.

RATIO SIGN.

Runs

6680.85

2 3340.4

3.29

no

Grain Size

857.59

4

214.4 .21 no

Interaction 9986.82

8

1248.4

1.23

no

Error

31429.

ll"

31

TOTAL

48954.37

45

-,

ANOVA - FIG

#12

c<= .05

response variable = period for completion of development

20g. sulfite - hydroquinone developer

SOURCE

r=-SS

\

MS RATIO SIGN.

Runs 1831.40

3

610.47

2.32 no

Grain Sizes

63.927

4

15.98 .061 no

Interaction

5672.5

12

472.71

1.80 no

Error 9993.2 38 262.98

20

ANOVA - FIG

#13

oC= .05

response variable = _initiation period

0.5g

sulfite developer vs.

20g

sulfite developer

A

M

SOURCE SS

t

i -

-MS RATIO SIGN.

Developers.

8528.5

1

8528.5

17.09

yes

Error

898O.

1 18

498.9

TOTAL

1,1 _iJ

17508.5

19

, .

-. : w

ANOVA - FIG

#14

<^= .05

response variable = _period of complete development

0.5g

sulfite developer vs.

20g

sulfite developer

f" SOURCE 1 -SS 1 : ms > RATIO

SIGN,,,

' _Developers 16.2 1 16.2 _.113

y

no

Error 2562.6 18 142.36

Al

i

JA

Cu

4

Qi

CD

6

O

n

SUMMARY AND CONCLUSIONS

The sensitometric curves do show, on a macroscopic scale,

a significant sensitometric difference betwen the two

developers.

Through the use of the statistical

tool,

the analysis of

variance it was determined that there was no significant

difference between runs for either developer using the

initiation period or the period of complete development as

response variables.

There were no functional relationships between grain sizes

and initiation periods for the

0.5g

and

20g.

sulfite hydro

quinone

developers,

nor were there functional relationships

between grain sizes and periods of complete development for

the same developers.

There is a significant difference between the

0.5g

sulfite

developer and the

20g

sulfite developer with respect to

initiation period. The average initiation period: for the

0.5g

sulfite is

44

sec. as compared with the

83

sec. average

initiation period for the

20g

sulfite. Turbide and Williams

24

increased

the Initiation period

decreased.

A guess as to why the

difference

might be explained

by

the difference in

development

mechanism for the two developers

(Figs.

15

& 16). There Is no significant difference between the

0.5g

sulfite

developer

and the

20g

sulfite developer with respect to

period of complete

development.

Dr. Eger described two types of development which are

dependent

upon the composition of the developer and to some

extent on the exposure conditions. The first type is the

"accretion development"

which spreads throughout the grain

from one or a few initiation points. Accretion development

occurred when there was a small number of active nuclei and

the developer showed marked initiation period. Accretion

development was noticed in the runs for the

20g

sulfite-hydroquinone developer. The second type is

Dr.

Eger's

"infectious development" in which protruberances from one

developing

grain start development in another. This defi

nition of "infectious development" was not seen in the runs

for the

0.5g

sulfite developer.

The litho type developer attained a greater gamma as compared

with the normal hydroquinone developer after 1 minute deve

lopment. This suggests that the rate of development for the

litho developer is greater than for the normal

developer.

This agrees with our previous results, the litho developer had

The results of this evaluation are useful only as an example of a possible statistical analysis for films of

a similar nature. This particular emulsion has definite

drawbacks- _{its large grains} are not typical of practical emulsions, and it is not _chemically sensitized.

26

LITERATURE REFERENCES

Hans

Eger,

"Infrared Microcinematographic and radio

chemical investigations of Photographic

Develop

ment,"

Dissertation,

Teoh. Hochschule

Munchen,

1969.

2Gorokhovskii

,

Polovtseva,

Shamsheva,

Ushechi

Nauchn,

"Kinetics of the Initial Stage of Photographic Dev

elopment,"

FOT

13 3041,

I968.

^Zwicky,

H.

, "The Mechanism of Litho

Development,"

Photo.

Korr.

v.

107,

1971.

^James,

T.H. , "The charge Effect in Relation to the Kinetics

of Photographic Development

III,

The Abnormal Behavior of Sulfite-Free Caustic

HQ

Developers,"

j.

Franklin Inst.

240,

1945.

*James,

T.H.,

"The Initiation of Development,*'

J.

-Photo. Sci.

vl9,

1971.

Karrer,

J.,

Berg W.F.,

"The Induction Period of Photographic

Development," _{SPSE Conference}

Summary,

May

1970.

7

'Zwicky,

H. , "Some Studies of Litho

Development,"

Photo.

Korr.,

1966.

p

Jaenicke,

W. , "Mechanism of the Development of Single

Grains,"

Photographic Science,

Zurich,

I96I.

"Meidinger,

"Studies of the Photographic Development Process,"

Physik z36, 1935.

10Frotschner,

H.

, Photogr.

Korr.,

27.

801,

1937.